Glycerol Polyglycidyl Ether Research Articles

Properties of soybean-flour-based adhesives enhanced by attapulgite and glycerol polyglycidyl ether

Soybean-flour (SF)-based adhesives were prepared using renewable glycerol polyglycidyl ether (GPE) as a cross-linking agent and low-cost attapulgite (ATP) as an enhancer to provide an excellent soy protein adhesive for the plywood industry. The shear strength, solid content, rheology, crystallinity, infrared spectra and morphological properties of the ATP modified SF (AMSF) adhesives were investigated in detail. The results indicated that the shear strength and water resistance of the AMSF adhesives improved significantly. The viscosity and solid content of the MSF adhesive increased when ATP was introduced, and these parameters could meet the requirement set by the China National Standard and ANSI/HPVA HP-1-2000, meanwhile. The crystallinity, infrared spectra, and morphology of AMSF indicated that no chemical reaction occurred between ATP and the modified soybean-flour (MSF) adhesive. The ATP acted as a bridge joint due to its rod-like structure that was inserted in the MSF adhesive and used as a physical bond to increase the shear strength of the AMSF adhesive. After ATP was introduced, the fracture surface of the cured AMSF adhesive became smoother and more compact. The AMSF adhesive is potentially independent of petrochemicals, formaldehyde-free, easy to use and readily available, which will promote the industrialisation of soy protein adhesives.

A new soy flour-polyepoxide adhesive system for making interior plywood

Abstract In this study, triglycidylamine (TGA) was synthesized and evaluated as a crosslinking agent for soy flour (SF) for making five-ply plywood from yellow poplar. Glycerol polyglycidyl ether (GPE) and trimethylolpropane triglycidyl ether (TTE) were also investigated as crosslinking agents for SF as adhesive for plywood. The plywood panels bonded with SF-TGA and SF-GPE adhesives did meet and those with SF-TTE adhesive did not meet the water-resistance requirement for interior application. The former two adhesives are formaldehyde-free, environmentally friendly, easy to use and readily available. They can be derived completely from renewable materials. The adhesion mechanisms are discussed in detail.

Preparation and characterization of large-size halloysite nanotubes particles by a combined technique of interfacial polymerization and condensation polymerization

To granulate halloysite nanotubes (HNTs) into large-size particles, interfacial polymerization and condensation polymerization were combined. The former was used to form surface layer of particles and the latter was used to improve particle strength. Polyethylenimine (PEI) and terephthaloyl chloride were chosen, respectively as hydrophilic monomer and hydrophobic monomer in interfacial polymerization. Condensation polymerization was carried out between PEI and glycerol polyglycidyl ether (GPE). The results show that HNTs particles have sphere shape and its diameters range from 1.7 to 2.5 mm and vary with preparation condition. SEM images show that particles have typical core–shell structure with dense surface layer and porous inner structure and single nanotube is completely encapsulated by polymer material. The characterization of BET shows that because of dense surface layer and encapsulation of nanotubes, the specific surface area of particles determined decreases dramatically.

Preparation and properties of biocomposites composed of glycerol‐based epoxy resins, tannic acid, and wood flour

AbstractAfter polyglycerol polyglycidyl ether (PGPE) and glycerol polyglycidyl ether (GPE) were mixed with tannic acid (TA) in ethanol and without solvent at epoxy/hydroxyl ratio 1/1, the obtained GPE‐TA and PGPE‐TA solutions were mixed with wood flour (WF), prepolymerized at 50°C, and subsequently compressed at 160°C for 3 h to give GPE‐TA/WF and PGPE‐TA/WF biocomposites with WF content 50–70 wt %, respectively. The storage moduli of the biocomposites in the rubbery state at more than 80°C were much higher than that of the control cured resins. The PGPE‐TA/WF composites had higher tensile modulus and rather lower tensile strength than PGPE‐TA. On the other hand, both the tensile modulus and strength of GPE‐TA/WF were much higher than those of GPE‐TA (2.4 GPa and 37 MPa). Those values of GPE‐TA/WF increased with WF content, became maximal values (5.1 GPa and 51 MPa) at WF content 60 wt %, and were lowered at 70 wt %. FE‐SEM analysis of the fractured surface of the biocomposites revealed that WF is tightly incorporated into the crosslinked epoxy resins. As a result of optimization of the epoxy/hydroxyl molar ratio for GPE‐TA/WF composite with WF content 60 wt %, the composite prepared at the ratio of 1.0/0.8 showed the highest tensile modulus and strength. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

A novel method of modifying poly(ethylene terephthalate) fabric using supercritical carbon dioxide

AbstractFor the modification of poly(ethylene terephthalate) (PET) fabric, a type of epoxy compound, glycerol polyglycidyl ether (GPE), was impregnated as a cross‐linking agent into PET fabric by means of supercritical carbon dioxide (scCO2), then, a series of immobilization processes were implemented, including the pad‐dry‐cure process and the solution process to finish the GPE‐PET fabric with natural functional agents (sericin, collagen, or chitosan). Chloroform was found to be an effective cosolvent, as evidenced by the mass transfer of GPE to PET during the treatment with scCO2. Chemical analyses by X‐ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy showed that GPE can penetrate the surface of the PET fabric in scCO2 pretreatment process, and natural functional agents (sericin, collagen, or chitosan) can also be immobilized on the surface of the GPE‐PET fabric especially for the method of pad‐dry‐cure. The nitrogen content in the modified PET fabrics was calculated accurately and confirmed by combustion analysis. The modified PET fabric displayed improvements in surface wettability, moisturization efficiency, and antibacterial characteristics against S. aureus, which demonstrated that the feasibility of this design for immobilizing natural functional agents (sericin, collagen, or chitosan) onto the surface of the PET fabric. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

Preparation and properties of biocomposites composed of bio‐based epoxy resin, tannic acid, and microfibrillated cellulose

AbstractAs new bio‐based epoxy resin systems, glycerol polyglycidyl ether (GPE) and sorbitol polyglycidyl ether (SPE) were cured with tannic acid (TA) at various conditions. When the curing conditions were optimized for the improvement of thermal and mechanical properties, the most balanced properties were obtained for the GPE/TA and SPE/TA cured at 160 °C for 2–3 h at the epoxy/hydroxyl ratio of 1/1. The cured SPE/TA had a higher glass transition temperature (Tg) and tensile strength than the cured GPE/TA. Next, biocomposites of GPE/TA and SPE/TA with microfibrillated cellulose (MFC) were prepared by mixing aqueous solution of the epoxy/curing reagent with MFC, and subsequent drying and curing at the optimized condition. For both the GPE/TA/MFC and SPE/TA/MFC biocomposites, Tg and the storage modulus at rubbery plateau region increased with increasing MFC content over the studied range of 3–15 wt %. The tensile strength at 25 °C for GPE/TA/MFC biocomposite with MFC content 10 wt % was 76% higher than that of control GPE/TA, while the tensile modulus was little improved. On the other hand, the tensile strength and modulus of SPE/TA/MFC biocomposite with MFC content 10 wt % were 30 and 55% higher than those of control SPE/TA, respectively. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 425–433, 2010

Flame Retardancy of Cellulose Fabrics Treated with 3-(Hydroxyphenyl Phosphinyl) Propanoic Acid

3-(Hydroxyphenyl phosphinyl) propanoic acid (HPPA) has been one of the most commonly used durable flame retardant agents for polyethylene terephthalate (PET) for many years. We intended to explore the application of HPPA to cellulose fabrics as formaldehyde-free phosphorus based flame retardants (FRs) through green chemistry process. The flame retardancy of the flame-retardant treated cellulose fabrics were characterized by using inductively coupled plasma spectroscopy (ICP) and limiting oxygen index (LOI). Structural changes of the treated cellulose fabrics were carried out by thermogravimetric analysis (TGA) and Fourier transform infrared (FT-IR) spectroscopy. To enhance the flame retardancy of HPPA treated cellulose fibers, glycerol polyglycidyl ether (GPE), a crosslinking agent was employed. Both HPPA and GPE treated cotton fabric imparted an LOI value over 26.

Investigation of New Epoxy Resins for the Gel Casting of Ceramics

Four water‐soluble epoxy resins that might be useful for aqueous gelation in an air atmosphere were studied for the gel casting of ceramics. The investigation was mainly focused on aspects of solubility, viscosity, suspension viscosity, and gelled body properties. The results demonstrated that ethylene glycol diglycidyl ether (EGDGE) and glycerol polyglycidyl ether (GPGE) were excellent for the gel casting of ceramics, and that polyethylene glycol diglycidyl ether and resorcinol diglycidyl ether were not suitable under the tested experimental conditions. The addition of 0.25 mL/g hardener was preferable for both EGDGE and GPGE.

An historical cohort mortality study of synthetic fiber workers potentially exposed to glycerol polyglycidyl ether.

We report an update of the mortality experience of a cohort of 8878 employees who worked between November 1, 1965, and December 31, 1988, at a synthetic fiber manufacturing facility with potential exposure to glycerol polyglycidyl ether (T55) and were followed through December 31, 1998. The mortality experience of the race/gender groups within the cohort was strikingly similar, with both the all causes of death and all cancer causes of death below unity on both national and local standards. For white men, there were no statistically significant increases for any cause of death, with the exception of benign neoplasms. Thirty-four percent of the cohort had worked at the plant for less than 1 year. Standardized mortality ratios were compiled for those with less than 1 year of employment and for those with 1 year or more of employment. Exclusion of those cohort members who worked less than 1 year had little impact on the standardized mortality ratios.

Penetration of Multifunctional Epoxide into Wool and Its Effect on Shrink Resistance

Wool fibers are treated with hydrophilic multifunctional epoxides (glycerol polyglyci dyl ether—GPE) under different reaction conditions, i.e., in saturated aqueous NaCl solution (sample S) and in the absence of NaCl (sample W). Add-on percentages of both samples are almost equal, but shrink-resistant properties are different for these two samples: the shrink resistance of sample W does not improved, while that of sample S improves significantly. TEM investigations of the cross sections of these samples stained with AgNO3 reveal remarkable morphological differences.

Crosslinking of Wool with Epoxide

Wool fabric is treated with a simple pad-dry-cure process using glycerol polyglycidyl ether, a multifunctional epoxide, to improve wrinkle recovery. Crosslinked samples with different add-ons are obtained by varying the epoxide concentration in the reaction system. Crosslinking of wool with epoxide is indirectly demonstrated by a solubility test, SEM, and FT-IR spectrometry. The crystalline structure of the crosslinked wool fabric remains unchanged, despite epoxide treatment. Moisture regain is reduced as epoxide concentration increases. Chemically modified wool fabrics show improved wet and dry wrinkle recovery behavior due to crosslinking. The effect of crosslinking on the glass transition temperature ( Tg) of wool is investigated using differential scanning calorimetry. The Tg of dry wool is predicted by plotting the reciprocal of Tg as a function of the water weight fraction using the Fox equation. The Tg of the samples increases with crosslinking. A thermomechanical analysis confirms that although the temperature of the final contraction peak of the crosslinked wool samples is similar to that of the untreated sample, it drops substantially above 20% epoxide concentration, suggesting less thermal stability.

Application of coacervated alpha-elastin to arterial prostheses for inhibition of anastomotic intimal hyperplasia.

Prevention of anastomotic intimal hyperplasia (AIH) requires inhibition of the migration of smooth muscle cells (SMCs) and promotion of endothelial cell (ECs) growth from the native arterial wall. We investigated the effect of coacervated alpha-elastin on migration of SMCs and ECs in vitro. SMCs and ECs were prepared from porcine aortic media and endothelium. Coacervated alpha-elastin was coated and cross-linked around the perimeter of each 1 cm diameter center of a well in a 12 well plate. SMCs and ECs were placed and cultured within the center of each well. The migration of SMCs and ECs on coacervated alpha-elastin was assayed on the second, third (10 mg/ml), or fourth day (0.1, 1.0, 10.0 mg/ml) of cultivation by measuring the area of migration from the 1 cm diameter center. Coacervated alpha-elastin was then coated and cross-linked on a Dacron graft using 1% glycerol polyglycidyl ether (GPGE) and examined with scanning electron microscopy to determine the feasibility of graft coating. SMC migration was significantly inhibited dose dependently over time (p < 0.005), e.g., 0.1 mg/ml (45.4% +/- 2.7%: % of MES [pH 5] and 1% GPGE without alpha-elastin), 1.0 mg/ml (32.0% +/- 1.4%), 10.0 mg/ml (8.3% +/- 2.9%). EC migration (90.7% +/- 6.2%: p = ns) was not inhibited by 0.1 mg/ml of coacervated alpha-elastin. Cross-linked coacervated alpha-elastin was coated on a dacron graft uniformly. Incorporation of coacervated alpha-elastin into the structure of arterial prostheses offers the possibility of inhibition of SMC hyperplasia without inhibition of EC formation.

Physical Properties of Wool Treated with Multifunctional Epoxides

We have investigated the physical properties of tropical wool fabrics. Samples were woven with yam from loose fibers treated with a water soluble multifunctional epoxide, i.e., glycerol polyglycidyl ether (GPE) in an aqueous medium catalyzed with a reductive agent (Na2S2O5) in the presence and absence of saturated NaCl. The resin treatment stiffened the fabrics somewhat and decreased their ability to regain moisture a little. Scanning electron microscopy revealed a difference in the abrasive breakdown pattern between the GPE/saturated aqueous NaCl treated wool and the untreated one. A good state of preservation of the hydrophobic nature of the scale surface after treatment was confirmed by soiling measurements of the wool with an oleophilic mixture/carbon black complex. There were fewer carbon black particle deposits in surfactant solution on the untreated and GPE/saturated aqueous NaCl treated wool than on the GPE/ H2O treated wool.

Shrink-Resistant Properties and Surface Characteristics of Wool Fibers Treated with Multifunctional Epoxides

Shrink-resistant properties and surface characteristics were investigated for wool fibers treated with hydrophilic multifunctional epoxides (glycerol polyglycidyl ether—GPE). Two different reaction conditions were used for the treatment, one in a saturated NaCl aqueous solution (S sample ) and the other in the absence of NaCl (W sample). Add- on percentages of both samples were almost the same. On the other hand, both shrink- resistant properties and surface characteristics were different for these two samples, showing that the reaction medium strongly affected the reaction mode of GPE. The degree of shrink-resistance of the W sample did not improve, while that of the S sample was much improved and almost equal to Cl/Hercostt (commercially) treated wool fibers. FTIR analyses showed that the surface concentration of GPE in the S sample was lower than that in the W sample, reflecting that the hydrophobic nature of the scale surface was maintained for the S sample and not the W sample. SEM observation results revealed prominent scale edges for the W sample but not for the S sample. These results explain the differences in shrink-resistant properties for the two samples.

A new antithrombogenic RV-PA valved conduit.

A new antithrombogenic right ventricular (RV)-pulmonary artery (PA) valved conduit was developed using a bovine jugular vein containing a natural valve. To maintain the natural and mechanical properties of the venous tissue, a hydrophilic cross-linking reagent, glycerol polyglycidyl ether polyepoxy compound (PC) was used instead of glutaraldehyde (GA). Moreover, to induce antithrombogenicity, heparin was bonded to the inner surface of the bovine jugular vein cross-linked with PC. Conduits of 18 to 20 mm inner diameter (ID) were implanted between the RV and PA in nine dogs weighing 7-17 kg, with the native main PA being ligated proximally. The handling and suturing of the graft was easy and adaptable, and the anastomosis was completed with excellent coaptation and no blood leakage at the suture lines. All animals were chronic survivors, but one animal died of hematemesis on the 438th postoperative day. Grafts were explanted from 182 to 385 days after implantation. The luminal surface of the conduits were white, glistening, and smooth with good coaptation of the cusps, without calcification or degenerative changes except for one cusp that showed a minimal deformation with a small thrombus. Macroscopic and microscopic observation showed that there were no thrombi at the anastomotic lines, but small thrombi on the luminal surface of the conduits near the cusps and in some cusps. Endothelium-like cells were noticed on the luminal surface of the graft, except in the area near the cusps, and on one cusp at 196 days after surgery. These results indicated that the new RV-PA valved conduit provided adequate antithrombogenicity by temporary slow heparin release, followed later by endothelialization of the graft in a low pressure system at 1 year after implantation.

Mortality among synthetic fiber workers exposed to glycerol polyglycidyl ether

We studied mortality among 8,878 employees who worked at any time from 1965 to 1988 at a synthetic fibers plant in North Carolina that used a finishing agent containing glycerol polyglycidyl ether. Some glycidyl ethers are mutagenic and tumorigenic in laboratory animals. The main route of exposure to workers was inhalation of the spray mist, although there was also skin contact. We identified 553 deaths in the cohort and the standardized mortality ratio (SMR) from all causes of death combined was 0.80. For most causes of death, mortality rates in the cohort were similar to mortality rates in the U.S. population. Among categories with at least five observed deaths, the largest effect estimate was for cancer of the central nervous system (SMR = 1.77), and the SMR for lung cancer was 0.94. The cancer categories of central nervous system (brain) and "other" lymphopoietic cancers (lymphoma and myeloma) showed weak associations with duration of employment. In case-control analyses in which we utilized work history data to compute effect estimates by duration of exposure, we found no increased risk of lung cancer or brain cancer among employees with more than 5 years of exposure. Effect estimates for lymphoma and myeloma tended to increase with duration of exposure, although there were only seven deaths in this category and the effect estimates were very imprecise. To date, this study has identified no clear carcinogenic effect of glycerol polyglycidyl ether, but plausible induction periods have not yet elapsed. The cohort should continue to be monitored to obtain more precise estimates after moderate or long induction times.

Development of bilayered gelatin substrate for bioskin: a new structural framework of the skin composed of porous dermal matrix and thin basement membrane

Extracellular matrices (ECM) of the skin are the structural framework of the epidermis and dermis (the substrate for cell adhesion) and are composed of both interstitial dermal components and the basement membrane. The technology for constructing ECM frameworks for the artificial skin was developed using gelatin as the principal material because of its high affinity and growth-promoting activity for skin cells. The skin framework was prepared through a sequential process containing four steps: solutions of gelatin and glycerol polyglycidyl ether (a cross-linker) were placed on the plate of polymethyl methacrylate and gelated by cooling the plate, then anisotropically frozen from the plate side. They were then lyophylized and finally were subject to heat treatment. The product was a bilayered matrix composed of porous dermal sponges and thin basement-membrane like structures. Conditions for preparing the skin matrix were optimized by changing several parameters in the process such as amounts of the cross-linker, gelation time, materials of the plate, freezing temperature, and conditions of heat treatment. The matrix thus obtained showed high affinities for epidermal cells and dermal fibroblasts and well populated by these cell with skin-like three-dimensional arrangement.

Evaluation of Epoxy Ether Fixed Bovine Arterial Grafts for Mutagenic Potential

Two epoxy ether compounds [glycerol polyglycidyl ether (Denacol EX-313) and ethylene glycol diglycidyl ether (Denacol EX-810)] are under consideration as alternatives to glutaraldehyde for use in the processing of an arterial graft. The two are utilized as cross-linking and sterilant agents, respectively. Epoxy resins are multifunctional alkylating agents, and bifunctional alkylating epoxide solutions are known to be mutagenic. The correlation between mutagenic potential and carcinogenicity, in addition to evidence that diepoxides are carcinogenic in mice and rats, prompted the evaluation of the mutagenic potential of the epoxy treated, clinically rinsed graft. Ames and sister chromatid exchange (SCE) test procedures were used to assess mutagenic potential. Normal saline and distilled water were selected as the most physiologically representative and procedurally acceptable extraction mediums for the Ames and SCE tests, respectively. The results of the Ames and SCE tests in both the activated and non activated systems indicated that there were no statistically significant differences detected between various test article concentrates and the spontaneous mutation controls for both the activated and non activated systems. The epoxy treated graft was determined to be non mutagenic and demonstrated no dose related responses by these methods.

A new RV-PA conduit with a natural valve made of bovine jugular vein.

A new RV-PA conduit with a natural valve was developed using bovine jugular vein. To maintain the natural, mechanical properties of the veins, a hydrophilic cross-linking reagent, a glycerol polyglycidyl ether polyepoxy compound (PC) was used. The treatment has already been proven in the field of vascular grafts to be able to reduce antigenicity, biodegradability, and degenerative changes such as calcification, to induce antithrombogenicity with hydrogenicity, and to improve affinity to host cells. Bovine jugular veins were cross-linked with the reagent and were implanted as a conduit into the RV-PA position in six dogs. The main PA was ligated after implantation. One animal died due to bleeding 2 days after implantation; the other animals were healthy and allowed to survive until they were sacrificed. The graft was very soft and as pliable as native tissue, and was as strong as a heart valve. Post-operative catheterization and angiography showed adequate function of the valve. Macroscopic and microscopic observations revealed the antithrombogenicity of the graft in this animal study. These results indicated that this newly developed biologic valved conduit has a high probability of overcoming many problems observed in existing RV-PA conduits.

Mechanical properties and immunogenicity of vascular xenografts

Polyepoxy compounds (PC) have been introduced as new cross-linking agents to overcome some of the disadvantages of glutaraldehyde (GA). In this study, we investigated the relationship of the reaction time to the immunogenicity and mechanical properties of canine and bovine common carotid arteries cross-linked with one of PC, namely, glycerol polyglycidyl ether (GPE). To evaluate mechanical properties, we made use of the finite deformation theory. Arteries cross-linked with GPE for 48 hours proved to be about 3 times as flexible as those cross-linked with GA for 48 hours. In the immunogenicity experiments, GPE was observed to reduce the immunogenicity of the arteries according to the reaction time, and the arteries, which were cross-linked with GPE for 48 hours, showed little immunogenicity. It was concluded that GPE is a more suitable cross-linking agent than GA, and its optimum reaction time seems to be 48 hours.